asc.wiley-vch.de
7.67 (s, 2 H, arom. H), 7.81 (dd, 2 H, 3J = 7.7 Hz, benzoyloxy-
H), 7.91 (dd, 2 H, 3J = 7.7 Hz, Iso-H); 13C NMR (100.6 MHz,
CDCl3/CD3OD, 25 °C): d = 18.8 (CH3), 23.2, 26.6, 35.8 (Cyh±
CH2), 45.6 (Cyh±Cq), 64.6 (trityl-Cq), 70.4 (OCH2), 113.7 (tri-
tyl-CH), 126.3, 126.9, 127.8, 127.8, 127.9, 131.4, 132.8 (CH),
125.5, 127.7, 128.8, 129.0, 130.3, 130.5, 131.2, 131.3, 131.9,
134.5, 134.7, 135.3, 135.4, 136.2, 141.0, 147.0, 148.9, 152.4,
156.2 (Cq), 165.4, 165.7 (C=O), 166.8 (COO); MALDI-MS: m/
z = 1824.1 [M+ + Na], 1840.3 [M+ + K]; FAB-MS: m/z = 1800.0
[M+], 1464.6 [M+ ± 1 stopper], 1127.4 [M+ ± 2 stopper], 1025.4
[M+ ± axle].
5-(Benzoyloxy)isophthaloyl Dichloride 8
4.0 g (14 mmol) of 5-benzoyloxyisophthalic acid were
heated under reflux for two hours in 50 mL (0.69 mol) thio-
nyl chloride with addition of 2 drops of dimethylformamide.
An excess of thionyl chloride was removed by distillation
and the product was crystallized from petroleum ether (60±
80 °C); mp 95 °C; yield: 0.9 g (19%); 1H NMR (250 MHz,
CDCl3, 25 °C): d = 7.55 (t, 3J = 7.4 Hz, 2H, benzoyloxy-H),
7.70 (d, 3J = 7.4 Hz, 2 H, benzoyloxy-H), 8.19 (t, 3J = 7.2 Hz,
1 H, benzoyloxy-H), 8.28 (s, 2H, Iso-H), 8.74 (s, 1 H, Iso-H);
13C NMR (62.9 MHz, CDCl3, 25 °C): d = 128.9, 130.4, 130.5,
130.6, 134.5 (CH), 128.0, 135.5 (Cq), 151.6 (C±O), 164.3
(COCl), 166.5 (C=O); FAB-MS: m/z = 321.6 [M+], 286.9 [M+
Cl].
±
Rotaxane 13 with Unprotected Wheel
268.3 mg (0.15 mmol) protected rotaxane 12 were heated in
40 mL dioxane and 20 mL water, with addition of 180.0 mg
(3.21 mmol) potassium hydroxide, for eight hours. The sol-
vents were removed by distillation and the residue was dis-
solved in 2 mL water. With concentrated hydrochloric acid
the solution was acidified until pH = 1. The formed precipi-
tate was dissolved in chloroform/ethyl acetate and the sepa-
rated organic phase washed with water several times and
dried over magnesium sulphate. The solvents were re-
moved by distillation and the product was dried at reduced
pressure; mp > 260 °C; yield: 234.4 mg (93%); 1H NMR
(250 MHz, CDCl3/CD3OD, 25 °C): d = 1.51 (br, 4 H, Cyh±
CH2), 1.61 (br, 8 H, Cyh±CH2), 1.87 (s, 24 H, CH3), 2.31 (br,
8 H, Cyh±CH2), 4.47 (s, 4 H, OCH2), 6.13 (s, 4 H, xylene-H),
6.41 (d, 4 H, 3J = 8.8 Hz, phenoxy-H), 7.02 (s, 8 H, arom. H),
7.05 (d, 4 H, 3J = 8.8 Hz, phenoxy-H), 7.11±7.21 (m, 30 H, tri-
tyl-H), 7.42 (s, 1 H, arom. H), 7.46 (s, 1 H, Iso-H), 7.59 (t, 1 H,
3J = 7.7 Hz, Iso-H), 7.79 (s, 2 H, arom. H), 8.00 (dd, 2 H,
3J = 7.7 Hz, 4J = 1.2 Hz, Iso-H); 13C NMR (62.9 MHz, CDCl3/
CD3OD, 25 °C): d = 18.9 (CH3), 23.3, 26.7, 35.9 (Cyh±CH2),
45.6 (Cyh-Cq), 64.7 (trityl-Cq), 70.5 (OCH2), 113.8 (trityl-
CH), 118.9, 126.4, 127.1, 127.9, 128.1, 132.0, 132.9, 134.8
(CH), 117.4, 131.4, 135.5, 136.3, 141.1, 147.1, 156.3 (Cq),
159.5 (COH), 167.2, 167.2 (C=O); MALDI-MS: m/z = 1718.4
[M+ + Na], 1734.5 [M+ + K].
Protected Tetralactam Macrocycle 10
0.84 g (2.58 mmol) 5-benzoyloxyisophthaloyl dichloride 8
were dissolved in 250 mL trichloromethane and 2.00 g
(2.58 mmol) N,N '-bis{4-[1-(4-amino-3,5-dimethylphenyl)cy-
clohexyl]-2,6-dimethylphenyl}isophthaloyl diamide 9 with
addition of 0.67 mL triethylamine were dissolved in 250 mL
trichloromethane. Both solutions were added simulta-
neously to 1.5 L of dichloromethane at room temperature
within eight hours. Afterwards the solvents were removed
by distillation and the product was purified using column
chromatography;
mp
302 °C;
Rf = 0.44
(CH2Cl2/
CH3CO2C2H5, 4/1); yield: 592 mg (22%); 1H NMR (250 MHz,
CDCl3/CD3OD, 25 °C): d = 1.30 (br, 4 H, Cyh-CH2), 1.41 (br,
8 H, Cyh±CH2), 1.95 (s, 24 H, CH3), 2.10 (br, 8 H, Cyh±CH2),
6.77 (s, 8 H, arom. H), 7.32 (t, 3J = 7.4 Hz, 2 H, benzoyloxy-
H), 7.42 (t, 3J = 7.7 Hz, 1 H, Iso-H), 7.45 (t, 3J = 7.4 Hz, 1 H,
benzoyloxy-H), 7.77 (s, 2H, arom. H), 7.88 (dd, 3J = 7.4 Hz,
4J = 1.4 Hz, 2 H, arom. H), 7.96 (d, 3J = 7.3 Hz, 2H, Iso-H),
8.06 (s, 1 H, arom. H), 8.11 (s, 1 H, Iso-H); 13C NMR
(62.9 MHz, CDCl3/CD3OD, 25 °C): d = 17.4, 17.9 (CH3), 22.5,
25.9, 34.9 (Cyh±CH2), 44.8 (Cyh±Cq), 123.8, 124.4, 125.9,
126.5, 128.4, 129.2, 129.8, 130.7, 133.8 (CH), 128.3, 130.8,
130.9, 134.1, 134.6, 135.8, 147.8, 151.5 (Cq), 164.9, 165.3,
166.5, 166.6 (C=O), 171.6 (COO); FAB-MS: m/z = 1025.6 [M+].
Rotaxane Assembly 14
9.0 mg potassium carbonate were suspended in a solution of
2.6 mg (0.009 mmol) 1,4-bis(bromomethyl)benzene 5,
8.6 mg (0.009 mmol) tetralactam wheel 6, and 30.2 mg
(0.018 mmol) rotaxane 13 in 9 mL chloroform. The mixture
was stirred for seven days at room temperature. After filtra-
tion the solvent was removed by distillation and the crude
product was purified by column chromatography;
mp > 250 °C; Rf = 0.30 (CH2Cl2/CH3CO2C2H5, 10/1); yield:
15.3 mg (39%); 1H NMR (400 MHz, CDCl3/CD3OD, 25 °C):
d = 1.30 (s, 9 H, C(CH3)3), 1.50 (br, 12 H, Cyh±CH2), 1.61 (br,
24 H, Cyh±CH2), 1.80±1.89 (m, 72 H, CH3), 2.30 (br, 24 H,
Cyh±CH2), 4.20 (s, 8 H, OCH2), 5.27 (s, 4 H, OCH2), 6.07 (s,
8 H, xylene-H), 6.14 (s, 4 H, xylene-H), 6.40 (d, 8 H,
3J = 8.8 Hz, phenoxy-H), 6.96±6.98 (m, 16 H, arom. H), 7.01
(d, 8 H, 3J = 8.8 Hz, phenoxy-H), 7.08±7.20 (m, 60 H, trityl-
H), 7.33±7.34 (m, 4 H, arom. H), 7.38 (s, 2 H, arom. H), 7.45
(t, 1 H, arom. H), 7.56 (m, 2 H, arom. H), 7.71 (s, 4 H, arom.
H), 7.72 (s, 2 H, arom. H), 7.86 (dd, 2H, 3J = 8.8 Hz, arom. H),
8.00±8.03 (m, 4 H, arom. H); 13C NMR (100.6 MHz, CDCl3/
CD3OD, 25 °C): d = 18.4, 20.7, 30.9, 31.7 (CH3), 22.8, 23.0,
Rotaxane 12
68.0 mg potassium carbonate were added to a solution of
51.5 mg (0.19 mmol) 1,4-bis(bromomethyl)benzene 5,
200.0 mg (0.19 mmol) of the protected tetralactam wheel
10, 7 mg (0.02 mmol) dibenzo[18]crown-6, and 131.3 mg
(0.39 mmol) p-tritylphenol 11 in 10 mL chloroform. The
mixture was stirred at room temperature for five days. After
filtration the organic phase was washed with water several
times and dried over magnesium sulphate. The solvent was
removed by distillation and purification of the product was
achieved by column chromatography; mp 307 °C; Rf = 0.29
(CHCl3/CH3CO2C2H5, 20/1); yield: 116.4 mg (33%); 1H NMR
(400 MHz, CDCl3/CD3OD, 25 °C): d = 1.29 (br, 4 H, Cyh±CH2),
1.41 (br, 8 H, Cyh±CH2), 1.68 (s, 24 H, CH3), 2.10 (br, 8 H,
Cyh±CH2), 4.06 (s, 4 H, OCH2), 5.95 (s, 4 H, xylene-H), 6.21
3
(d, 4 H, J = 8.8 Hz, phenoxy-H), 6.81 (s, 8 H, Ar±H), 6.84 (d,
4 H, 3J = 8.8 Hz, phenoxy-H), 6.92±7.02 (m, 30 H, trityl-H),
7.29 (t, 2 H, benzoyloxy-H), 7.37 (t, 1 H, Iso-H), 7.43 (t, 1 H,
benzoyloxy-H), 7.50 (s, 1 H, arom. H), 7.56 (s, 1 H, Iso-H),
308
Adv. Synth. Catal. 2001, 343, 303±309